JP3181048B1 - Fast-curing adhesive, method for producing fast-curing adhesive, and bonding method - Google Patents

Abstract

[Summary] [Problem] The curing speed is fast and there is no safety and health problem.
An object of the present invention is to provide a fast-curing adhesive which is easy to manufacture and requires less energy for manufacturing, a method for manufacturing the same, and a bonding method. SOLUTION: Water is added to 100 parts of an acrylic emulsion by 3 parts.
While adding 0 parts and stirring, 20 parts of acetoacetylated polyvinyl alcohol (degree of polymerization: about 1000) is gradually added as powder. Stirring is continued for another 3 hours after the temperature of the mixture reaches 60 ° C. by the heat of mixing. After confirming dissolution of the acetoacetylated polyvinyl alcohol, the mixture was cooled to room temperature to obtain an adhesive composition having a resin concentration of 50% by weight, which was used as a first agent. Also, 100 parts of a 10% by weight aqueous solution of adipic dihydrazide and 20 parts of a 20% by weight aqueous solution of lithium chloride were mixed to prepare a second agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-pack application type quick-curing adhesive, and more particularly, to a door or panel manufactured by flash bonding or V-cut bonding between a core material and a surface material, or a plurality of doors and panels. The present invention relates to a two-pack application type fast-curing adhesive used in the wood processing industry, such as glued laminated wood, which is produced by bonding two pieces of lamina, a method of manufacturing the same, and a method of bonding the same.

[0002]

2. Description of the Related Art In the wood processing industry, there has been an attempt to mass-produce wood products by making a production process continuous by a conveyor system. For this reason, an adhesive having a high initial adhesive force and a high bonding speed has been demanded. ing.

As an adhesive used for the purpose, a cyanoacrylate-based instant adhesive or a urea resin-based adhesive is used as a first agent, and a strong acid such as phosphoric acid is mixed with an aqueous solution of a polymer compound such as polyvinyl alcohol. There is a two-component, separate-coating, quick-setting adhesive used as the second agent.

JP-B-63-17871 discloses a first agent comprising an aqueous solution of a soluble protein having an amide bond in the molecule or an aqueous solution of a synthetic polymer having an imide group and an aqueous emulsion. A fast-curing adhesive composition comprising an aqueous solution of a dialdehyde compound and a second agent is disclosed.

Furthermore, Japanese Patent Publication No. 1-60190 discloses a first agent comprising an aqueous solution and / or an aqueous emulsion of a polymer compound having an acetoacetyl group in a molecule, and a second agent comprising an aqueous solution of an aldehyde compound. And a method of bonding the same.

Japanese Patent Publication No. 1-60192 discloses a first agent comprising an aqueous solution and / or emulsion of a polymer compound having an acetoacetyl group in a molecule, and an aqueous solution of a hydrazine compound. There are disclosed an instant-curing aqueous adhesive composed of two components and an adhesive method by two-liquid separation.

Specifically, as a first agent, a polymer compound having an acetoacetyl group is dissolved in advance as an aqueous solution, and an aqueous solution and / or emulsion of the polymer compound is mixed therein. Things and
A polymer produced by using a polymer compound having an acetoacetyl group as a protective colloid or an emulsifier and performing emulsion polymerization of vinyl acetate or the like is disclosed.

[0008]

However, the above-mentioned two-component separation coating type adhesive has the following disadvantages. Since the cyanoacrylate-based instant adhesive is expensive, it is unavoidable to increase the price of the product when applied to a large area, and it is not practical.

An adhesive in which a urea resin-based adhesive is used as a first agent, and a strong acid such as phosphoric acid is mixed with an aqueous solution of a polymer compound as a second agent, the strong acid promotes the aging properties of the urea resin system, There is a disadvantage that the strength of the wood itself is deteriorated. A two-part separation coating type adhesive composition utilizing crosslinking and curing of a polymer having an imide group in the molecule and a dialdehyde,
Since the cross-linking curing is reversible curing by heat, there is a problem in durability. In addition, glyoxal, which is a representative of dialdehyde compounds, is a designated substance according to the PRTR method or the like, and has a problem in safety and health.

An aqueous adhesive composition comprising a first agent comprising an aqueous solution and / or an aqueous emulsion of a polymer compound having an acetoacetyl group in a molecule and a second agent comprising an aqueous solution of an aldehyde compound has a curing rate of And the curing speed in about 30 seconds desired by the user cannot be obtained.

A flash-curable aqueous adhesive composition comprising a first agent comprising an aqueous solution and / or an aqueous emulsion of a polymer compound having an acetoacetyl group in a molecule and a second agent comprising an aqueous solution of a hydrazine compound is However, depending on the type, there are the following disadvantages.

The first agent is prepared by dissolving a polymer compound having an acetoacetyl group as an aqueous solution in advance and mixing an aqueous solution and / or aqueous emulsion of the polymer compound therein. It was difficult to obtain an adhesive composition having a high resin concentration suitable for time bonding, and it was particularly difficult to increase the resin concentration by mixing acetoacetylated polyvinyl alcohol having a polymerization degree of 1000 or more at a high ratio. Therefore, the obtained adhesive has a low effective resin concentration, and it is difficult to obtain an initial adhesive strength that can be used.

In the case where the first agent is produced by emulsion polymerization of vinyl acetate and the like using a polymer compound having an acetoacetyl group as a protective colloid or an emulsifier, it is possible to increase the resin concentration. Since the acetoacetyl group also enters the emulsion particles, the reactivity with the hydrazine compound is poor, and the obtained adhesive has a low curing speed, and it is difficult to obtain an initial adhesive strength that can be used.

For this reason, when flash bonding, V-cut bonding, kneading bonding, etc. are performed by pressing for a short time of 30 seconds using the adhesive composition, a sufficient initial adhesive force cannot be obtained, Immediately after decompression, adhesion failure such as peeling occurred. The present invention has been made in view of the above points, the curing speed is fast, there is no safety and health problems,
An object of the present invention is to provide a fast-curing adhesive which is easy to manufacture and requires less energy for manufacturing, a method for manufacturing the same, and a bonding method.

[0015]

Means for Solving the Problems and Effects of the Invention (1) The invention of claim 1 comprises a first agent containing a resin emulsion and acetoacetylated polyvinyl alcohol, and a second agent containing a hydrazine derivative. A quick-curing adhesive, wherein the sum of the weight ratio of the resin emulsion in the first agent and the weight ratio of the acetoacetylated polyvinyl alcohol is in the range of 45 to 65% by weight, and A quick-curing adhesive characterized in that the degree of polymerization of polyvinyl alcohol is in the range of 1000 to 2500.

The quick-curing adhesive of the present invention comprises the sum of the weight ratio of the resin emulsion in the first part and the weight ratio of the acetoacetylated polyvinyl alcohol (resin concentration).
Is as high as 45 to 65% by weight, and the degree of polymerization of acetoacetylated polyvinyl alcohol is 1000 to 2500.
Therefore, it has sufficient acetoacetyl groups effective for the adhesive reaction, and it is possible to obtain fast curing properties and high initial adhesive strength.

Therefore, the quick-curing adhesive of the present invention has a high curing speed and can obtain a high initial adhesive strength. Demonstrates satisfactory performance. In addition, the quick-curing adhesive of the present invention is manufactured by the PRTR method (Po
luluent Release and Trans
Since it does not contain the designated substances in the "Fer Register", it can be used without any problem on safety and health.

The resin emulsion includes, for example, a resin emulsion containing no acetoacetyl group. Specifically, a resin emulsion mainly containing a vinyl monomer such as vinyl acetate, acrylate or methacrylate is used. Emulsion polymers and synthetic resin emulsions such as emulsion-polymerized copolymers such as ethylene-vinyl acetate or acrylates, and synthetic rubbers such as natural rubber, isoprene rubber, styrene-butadiene rubber, butyl rubber, chloroprene rubber, and nitrile rubber There are a rubber latex which is an emulsion polymer and a modified rubber latex into which a functional group such as a carboxyl group is introduced, and these synthetic resin emulsions and rubber latexes can be used alone or in combination of two or more. Among them, an acrylic emulsion having excellent water resistance and light resistance is preferable.

The resin emulsion is, for example,
It may be a resin emulsion having an acetoacetyl group. However, in this case, it is preferable that at least a part contains a resin other than acetoacetylated polyvinyl alcohol. -The acetoacetylated polyvinyl alcohol is obtained, for example, by reacting polyvinyl alcohol with diketene.

The degree of polymerization of the acetoacetylated polyvinyl alcohol is from 1,000 to 2,500. Polymerization degree 100
If it is less than 0, the adhesive layer after reacting with the hydrazine derivative is soft and has low strength. If the degree of polymerization is 2500 or more, it is difficult to dissolve and it is difficult to produce an adhesive composition.

The degree of saponification of the acetoacetylated polyvinyl alcohol is preferably from 80 to 100 mol%. If the saponification degree is less than 80 mol%, it is difficult to dissolve, and it is difficult to produce an adhesive composition. If it exceeds 100 mol%, it cannot be produced. The degree of acetoacetylation modification of acetoacetylated polyvinyl alcohol is preferably from 3 to 20 mol%, particularly preferably from 4 to 10 mol%. When the degree of acetoacetylation modification is less than 3 mol%, the reaction rate with the hydrazine derivative becomes slow, and sufficient initial strength cannot be obtained. It is difficult to manufacture the composition.

The hydrazine derivative includes, for example, hydrazine, hydrazine hydrate, hydrazine hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid, thiocyanic acid, carbonic acid and other inorganic salts, and formic acid, oxalic acid and other organic acids; Hydrazine methyl, ethyl, propyl, butyl,
Monosubstituted such as allyl, asymmetric disubstituted such as 1,1-dimethyl, 1,1-diethyl, 4-n-butylmethyl, and
Symmetric disubstitutes such as 1,2-dimethyl, 1,2-diethyl, and 1,2-diisopropyl are exemplified.

Examples of the hydrazine derivative which can be used include, for example, adipic dihydrazide, carbodihydrazide, oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, sebacic dihydrazide, dodecane diacid dihydrazide, and isophthalic acid having a high reactivity with an acetoacetyl group. Acid dihydrazide, terephthalic acid dihydrazide,
Glycolic acid dihydrazide, polyacrylic acid dihydrazide and the like can be mentioned.

The second agent is, for example, an aqueous solution or an aqueous dispersion, and the concentration by weight of the hydrazine compound in the second agent is, for example, 0.1 to 50% by weight.
It is appropriately selected from the balance between the curing speed and the adhesive strength. -The first agent and / or the second agent may be used, if necessary, for example, fillers such as calcium carbonate, kaolin, and clay, plasticizers, preservatives, rust preventives, coloring agents, surfactants, and viscosity adjustment. Agents, catalysts, metal salts, and the like can be appropriately added.

(2) The invention according to claim 2 is characterized in that the first agent contains an isocyanate compound. The fast-curing adhesive of the present invention is excellent in water resistance after curing, for example, because the first component contains an isocyanate compound.

As the isocyanate compound, for example, phenylmethane diisocyanate (MD
I), isocyanate compounds such as tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and xylylene diisocyanate (XDI).

The compounding amount of the isocyanate compound may be, for example, other components of the first agent (for example, an aqueous solution of the resin emulsion and acetoacetylated polyvinyl alcohol).
It can be 5 to 40 parts per 100 parts, and preferably 10 to 25 parts. If it is less than 5 parts, it is difficult to obtain water resistance, and if it is more than 40 parts, the isocyanate reacts with water in the solution, resulting in poor storage stability.

(3) The invention according to claim 3 is a method for producing a fast-curing adhesive comprising a first agent containing a resin emulsion and acetoacetylated polyvinyl alcohol, and a second agent containing a hydrazine derivative. Wherein the step of producing the first agent comprises a step of stirring and mixing the powder of the acetoacetylated polyvinyl alcohol with the resin emulsion to dissolve the acetoacetylated polyvinyl alcohol in the mixture. The gist is a method of manufacturing an adhesive.

In the method for producing a fast-curing adhesive according to the present invention, the first component is produced, for example, by mixing powdery acetoacetylated polyvinyl alcohol with a resin emulsion while stirring. At this time, heat of mixing occurs due to mixing of the resin emulsion and acetoacetylated polyvinyl alcohol, and for example, the acetoacetylated polyvinyl alcohol is dissolved by the heat of mixing.

In the method for producing a fast-curing adhesive according to the present invention, for example, a mixture of a resin emulsion and powdery acetoacetylated polyvinyl alcohol is heated from outside to dissolve the acetoacetylated polyvinyl alcohol. can do.

Further, in the production method of the present invention, since the powdery acetoacetylated polyvinyl alcohol is used as a raw material in the production of the first part, the degree of polymerization of the acetoacetylated polyvinyl alcohol contained in the first part is increased. In addition, it is possible to increase the resin concentration of the first agent. Here, the resin concentration refers to the ratio of the resin to the total amount including the water in the adhesive composition.

That is, as in the conventional production method using an aqueous solution of acetoacetylated polyvinyl alcohol, the degree of polymerization of acetoacetylated polyvinyl alcohol contained in the first agent depends on the solubility limit of acetoacetylated polyvinyl alcohol in water. In addition, the resin concentration is not limited low.

Therefore, in the production method of the present invention, the degree of polymerization of the acetoacetylated polyvinyl alcohol contained in the first part is increased (for example, polyvinyl alcohol having a degree of polymerization of 1000 or more), and the resin concentration of the first part is increased. Is sufficiently high (for example, 45% by weight or more), it is possible to produce a fast curing adhesive having a high initial adhesive strength.

If the heat of mixing alone is not enough to dissolve the acetoacetylated polyvinyl alcohol, the mixture can be heated from the outside, for example. The second agent can be produced, for example, by dissolving a hydrazine derivative in water.

The resin emulsion may be produced by a polymerization reaction, or an off-the-shelf product (for example, Aika Aibon RAX-81L / Aika Kogyo Co., Ltd.) may be used. The first of the acetoacetylated polyvinyl alcohols;
The weight ratio with respect to the whole agent is preferably 5% by weight or more in order to accelerate the curing reaction and make the composition curable quickly.

In the mixing of the resin emulsion and the acetoacetylated polyvinyl alcohol, the mixture of the acetoacetylated polyvinyl alcohol should not
It is preferable to mix gradually while stirring. In addition, the mixing and stirring of the resin emulsion and the acetoacetylated polyvinyl alcohol are performed by using a high-speed rotatable stirring mixer with stirring blades, thereby increasing the viscosity of the mixture and generating sufficient heat of mixing. Can be done.

(4) According to a fourth aspect of the present invention, the quick-curing adhesive is the quick-curing adhesive according to the first or second aspect. The gist is a method for producing the agent. According to the production method of the present invention, it is possible to produce a fast-curing adhesive which has a high resin concentration of the first agent and a high degree of polymerization of acetoacetylated polyvinyl alcohol, and is excellent in quick-curing properties and initial adhesive strength.

Further, the quick-curing adhesive produced in the present invention is:
Since it does not contain the substances specified in the PRTR Law, it can be used without any problem on safety and health. (5) The invention of claim 5 has a gist of the method for producing a quick-setting adhesive according to claim 3 or 4, wherein the acetoacetylated polyvinyl alcohol is dissolved by heating.

In the manufacturing method of the present invention, the acetoacetylated polyvinyl alcohol powder mixed with the resin emulsion is dissolved by heating.
It can be performed by the heat of mixing generated by mixing the resin emulsion and the acetoacetylated polyvinyl alcohol.

In addition to the heat of mixing, for example, by externally applying heat to a container containing the mixture, the acetoacetylated polyvinyl alcohol can be sufficiently dissolved. (6) The invention according to claim 6 is characterized in that the heating is performed by internal mixing heat generated with the generation of the mixture, and the method for producing a quick-curing adhesive according to claim 5 is summarized. .

The present invention illustrates a method of heating. In the production method of the present invention, acetoacetylated polyvinyl alcohol is dissolved by heat of mixing generated by mixing the resin emulsion and acetoacetylated polyvinyl alcohol.

For this reason, external heating for dissolving the acetoacetylated polyvinyl alcohol in the mixture is unnecessary or requires only a small amount of heat. As a result, in the manufacturing process, resin tends to be generated due to heating of the mixture (a state in which the emulsion surface in contact with the air layer forms a film), and resin adheres to the inner wall of a kettle (a container that stores the mixture). Problems such as sticking can be solved, and energy required for manufacturing can be saved.

(7) The invention according to claim 7 is characterized in that:
A gist of the method for producing a quick-curing adhesive according to any one of claims 3 to 6, wherein an isocyanate is blended. Since the fast-curing adhesive produced in the present invention contains isocyanate, for example, it has excellent water resistance after curing.

The isocyanate can be added to the resin emulsion before mixing the resin emulsion with the acetoacetylated polyvinyl alcohol, for example.
After the mixing, the mixture can be added to a mixture of the resin emulsion and acetoacetylated polyvinyl alcohol.

The amount of the isocyanate compound is as follows:
For example, the amount can be 5 to 40 parts, and preferably 10 to 25 parts, per 100 parts of other components of the first agent (for example, an aqueous solution of the resin emulsion and acetoacetylated polyvinyl alcohol). If it is less than 5 parts, it is difficult to obtain water resistance, and if it is more than 40 parts, the isocyanate reacts with water in the solution, resulting in poor storage stability. (8) The invention according to claim 8 is a bonding method using the quick-curing adhesive according to claim 1 or 2, wherein the first agent is applied to a surface of one member and the second agent is applied. Applying the first agent to the surface of the other one member, so that the surface of the one member applied with the first agent and the surface of the other member applied with the second agent are overlapped. And a bonding step of bonding the one member and the another member to each other.

According to the bonding method of the present invention, for example, a sufficient final bonding strength can be obtained only by pressing the members for a short time after bonding the members. Further, the bonding method of the present invention has the advantage that the steps can be simplified because mixing of the first agent and the second agent is unnecessary.

The above-mentioned one member includes, for example, a particle board, and the other one member includes, for example, plywood. As a method of applying in the application step, for example, in addition to a method using an application device such as a brush or an automatic gluing machine, an adherend ( There is also a method of spraying and applying to one member or another member), for example, a method of applying with two spray guns or a double-head spray gun by an air spray or airless spray method.

The application amount of the first agent in the application step can be, for example, 10 to 300 g / m ² as a solid content, and the application amount of the second agent is 1 to 50 g as a hydrazine derivative.
/ M ² . In the bonding step, for example, the bonding force can be increased by pressing the members after bonding. (9) An invention according to claim 9 is the bonding method using the quick-curing adhesive according to claim 1 or 2, wherein the first agent and the second agent are sequentially arranged on the surface of one member. Depositing and applying the first member and the other member so that the surface of the one member on which the deposition application is performed is a surface to be bonded to another member. A bonding method characterized by including a bonding step of bonding.

According to the bonding method of the present invention, both the first agent and the second agent can be deposited and applied to only one member.
Bonding can be performed even if the other member has a shape that is difficult to apply the adhesive. In the bonding method of the present invention, for example, a sufficient final bonding strength can be obtained only by pressing the members for a short time after bonding the members.

Further, the bonding method of the present invention comprises the steps of:
Since the mixing with the agent is unnecessary, the process can be simplified. -As the one member, for example, there is a porous plate such as wood, plywood, verticle board, slate plate, etc., and as the other one member, for example, a porous material such as foam, paper, or veneer There is an adherend.

In the deposition application step, the first agent and the second agent can be applied using an application device such as a spray or a brush or an automatic gluing machine. The order of application of the first agent and the second agent may be, for example, first applying the first agent and then applying the second agent thereon, or applying the second agent first. The first agent may be applied thereon.

The application amount of the first agent in the deposition application step can be, for example, 10 to 300 g / m ² as a solid content, and the application amount of the second agent is 1 to 5 as a hydrazine derivative.
It can be 0 g / m ² .

[0053]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples (embodiments) of a fast-curing adhesive, a method for producing a fast-curing adhesive, and a bonding method according to the present invention will be described. a) The fast-curing adhesives of Examples 1 to 4 and Comparative Examples 1 to 7 will be described.

The quick-curing adhesives manufactured in Examples 1 to 4 and Comparative Examples 1 to 6 are composed of a first agent and a second agent.
The quick-setting adhesive prepared in Comparative Example 7 is a single-agent type adhesive. (Example 1) Acrylic emulsion (Aika Aibon R)
AX-81L / Aika Kogyo Co., Ltd.)
While adding 0 parts and stirring, 20 parts of acetoacetylated polyvinyl alcohol (Gosefimer Z-200, degree of polymerization: about 1000 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was gradually added as powder.

The viscosity and temperature increased with stirring, and the mixture was further stirred for 3 hours after the temperature of the mixture reached 60 ° C. After confirming dissolution of the acetoacetylated polyvinyl alcohol, the mixture was cooled to room temperature to obtain an adhesive composition having a resin concentration of 50% by weight. This was designated as a first agent.

Next, 100 parts of a 10% by weight aqueous solution of adipic dihydrazide, 20 parts by weight of an aqueous solution of lithium chloride 20
Parts were mixed to form a second agent. The first embodiment is an example within the scope of the invention described in claims 1 and 3 to 6. (Example 2) 40 parts of water was added to 100 parts of an ethylene vinyl acetate emulsion (Aika Aibon AE-21 / Aika Kogyo Co., Ltd.) and 30 parts of acetoacetylated polyvinyl alcohol (Gosefimer Z-200 /
Nippon Synthetic Chemical Industry Co., Ltd.) was gradually added as powder.

The viscosity and the temperature increased with stirring, and the mixture was stirred for 3 hours after the temperature of the mixture reached 60 ° C. After confirming dissolution of the acetoacetylated polyvinyl alcohol, the mixture was cooled to room temperature to obtain an adhesive composition having a resin concentration of 48% by weight. This was designated as a first agent. Next, 100 parts of a 10% by weight aqueous carbodihydrazide solution and 20 parts of a 20% by weight aqueous magnesium chloride solution were mixed to prepare a second agent.

The second embodiment is an example within the scope of the present invention. (Example 3) To 100 parts of the first agent of Example 1, 20 parts of isocyanate (AUH-1 / Aika Kogyo KK) was added to obtain an adhesive composition having a resin concentration of 58% by weight. This was designated as a first agent.

The second agent was the same as the second agent of Example 1. The third embodiment is an example within the scope of the invention described in claims 1 to 7. (Example 4) Acrylic emulsion (Aika Aibon RAX-81L / manufactured by Aika Kogyo) as a first agent 1
30 parts of water was added to 00 parts, and 20 parts of acetoacetylated polyvinyl alcohol (Gosefimer Z-200 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was powdered with stirring while applying forced heating from the outside with superheated steam. It was gradually added as it was.

After the temperature of the mixture reached 60 ° C., stirring was continued for another 3 hours. Then, after confirming dissolution of the acetoacetylated polyvinyl alcohol, the mixture was cooled to room temperature to obtain an adhesive composition having a resin concentration of 50% by weight. This was designated as a first agent. The second agent was the same as the first agent of Example 1.

It should be noted that the fourth embodiment is characterized in that:
This is an example that is within the scope of the present invention and outside the scope of the invention of claim 6. (Comparative Example 1) Acetoacetylated polyvinyl alcohol (Gosefimer Z-200 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was previously dissolved as a 20% by weight aqueous solution. Acrylic emulsion (Aika Aibon RAX-81L /
100 parts of an aqueous solution of 20% by weight of acetoacetylated polyvinyl alcohol was mixed with 100 parts of Aika Kogyo Co., Ltd. to obtain an adhesive composition having a resin concentration of 38% by weight. This was designated as a first agent.

Next, 100 parts of a 10% by weight aqueous solution of adipic dihydrazide and 20% by weight of an aqueous solution of lithium chloride 20
Was mixed to obtain a second agent. In Comparative Example 1, since the resin concentration of the first agent was 38% by weight, it was out of the scope of the invention of Claim 1, and the acetoacetylated polyvinyl alcohol powder was not used in the production method. Item 3 is outside the scope of the invention. (Comparative Example 2) Acetoacetylated polyvinyl alcohol (Gosefimer Z-200 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was previously dissolved as a 20% by weight aqueous solution. 100 parts of a 20% by weight acetoacetylated polyvinyl alcohol aqueous solution was mixed with 100 parts of a vinyl acetate emulsion (Aika Aibon A-370 / Aika Kogyo Co., Ltd.) to obtain an adhesive composition having a resin concentration of 38% by weight. Was. This was designated as a first agent.

Then, 100 parts of a 10% by weight aqueous solution of adipic dihydrazide, 20 parts by weight of an aqueous solution of lithium chloride 20
Parts were mixed to form a second agent. In Comparative Example 2, since the resin concentration of the first agent was 38% by weight, it was out of the scope of the invention of Claim 1, and the acetoacetylated polyvinyl alcohol powder was not used in the production method. Item 3 is outside the scope of the invention. (Comparative Example 3) Acetoacetylated polyvinyl alcohol (Gosefimer Z-100, degree of polymerization: about 500 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was previously dissolved as a 35% by weight aqueous solution. Vinyl acetate emulsion (Aika Aibon A
-344K / Aika Kogyo Co., Ltd.)
100 parts of a 5% by weight acetoacetylated polyvinyl alcohol aqueous solution was mixed to obtain an adhesive composition having a resin concentration of 43% by weight. This was designated as a first agent.

Next, 100 parts of a 10% by weight aqueous solution of adipic dihydrazide and 20 parts by weight of an aqueous solution of lithium chloride 20
Parts were mixed to form a second agent. In Comparative Example 3, since the degree of polymerization of the acetoacetylated polyvinyl alcohol contained in the first agent was 500, it was outside the scope of the invention of claim 1, and the powder of the acetoacetylated polyvinyl alcohol was used in the production method. Since the body is not used, it is outside the scope of the invention of claim 3. (Comparative Example 4) An emulsion having a resin concentration of 48% by weight obtained by emulsion polymerization using acetoacetylated polyvinyl alcohol (Gosefimer Z-200 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as an emulsifier was used as the first emulsion. Agent. Then, a 10% by weight aqueous solution of adipic dihydrazide 100
And 20 parts by weight of a 20% by weight aqueous solution of lithium chloride to obtain a second agent.

In Comparative Example 4, (added together with acetoacetylated polyvinyl alcohol) was added to the first agent.
Since a resin emulsion is not used, it is out of the scope of the invention of claim 1, and since no acetoacetylated polyvinyl alcohol powder is used in the production method, it is out of the scope of the invention of claim 3. (Comparative Example 5) Acetoacetylated polyvinyl alcohol (Gosefimer Z-200 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was previously dissolved as a 20% by weight aqueous solution. Acrylic emulsion (Aika Aibon RAX-81L /
100 parts of an aqueous solution of 20% by weight of acetoacetylated polyvinyl alcohol was mixed with 100 parts of Aika Kogyo Co., Ltd. to obtain an adhesive composition having a resin concentration of 38% by weight. This was designated as a first agent.

Next, a 40% by weight aqueous glyoxal solution was used as a second agent. In Comparative Example 5, since the resin concentration of the first agent was 38% by weight and the second agent did not contain a hydrazine derivative, it was out of the scope of the first aspect of the present invention. Since no vinyl alcohol powder is used, the present invention is out of the scope of the third aspect of the present invention. (Comparative Example 6) 20% by weight of an imide-modified isovan (IM-304 / Kuraray Co., Ltd.) containing an imide group in a molecule in advance.
Dissolved as an aqueous solution. Acrylic emulsion (Aika Aibon RAX-81L / Aika Kogyo) 100
Parts of a 20% by weight aqueous solution of imide-modified isovan
0 parts were mixed to obtain an adhesive composition having a resin concentration of 38% by weight.
This was designated as a first agent.

Next, a 40% by weight aqueous glyoxal solution was used as a second agent. Note that Comparative Example 6 is an example outside the scope of the present invention. (Comparative Example 7) An aqueous adhesive comprising a vinyl acetate emulsion (Aika Aibon A-344K, resin concentration: 53% by weight / manufactured by Aika Kogyo) was prepared.

Comparative Example 7 is an example outside the scope of the present invention. In addition, the manufacturing method of the fast-curing adhesive of Examples 1 to 4 and Comparative Examples 1 to 7, the degree of polymerization of acetoacetylated polyvinyl alcohol, the resin concentration of the first agent, and whether or not the substance specified by the PRTR method is 1% by weight or more. The results are shown in Table 1.

[0069]

[Table 1]

B) Next, Examples 1 to 4 and Comparative Examples 1 to 7
A test performed to confirm the effect of the quick-curing adhesive manufactured in the above will be described. Split adhesive strength test i) Test method The test was performed on the fast-curing adhesives of Examples 1 to 3 and Comparative Examples 1 to 7 by the method shown in JIS K 6853, "Test method for splitting adhesive strength of adhesive". The procedure was performed as follows.

Two pieces of plywood (32 mm × 25 mm) were used as adherends, the first agent was applied to one plywood at an application amount of about 150 g / m ² , and the other agent was applied to the other plywood at an application amount of about 30 g / m2. / M ²
After applying, both sides are stuck together and immediately about 0.5MP
The sample was pressed with a for 30 seconds to prepare a test body. This bonding method (both-side coating bonding method) is a method within the scope of claim 7.

In the fast-curing adhesive of Example 3, the second agent was first applied to one of the plywood at an application amount of about 30 g / m ² , and the first agent was applied thereon at an application amount of about 30 g / m ² . 150 g / m ²
And the other plywood was uncoated, and two pieces were stuck together in the same manner as above to produce a test piece pressed and pressed. This bonding method (one-sided application bonding method) is a method within the scope of claim 8.

Next, for each of the test pieces, after the test piece was prepared (that is, after the pressure was released from the press-clamping), the test piece was allowed to stand under the following three conditions, and then subjected to a split test. (The area ratio of the plywood to the to-be-adhered area) was measured. -Immediately after decompression of press compression (initial condition)-After curing at room temperature for 24 hours (leaving condition at room temperature for 24 hours)-After curing at room temperature for 24 hours, then immerse in 60 ° C water for 3 hours, then wet Immediately as it is (24 hours at room temperature + hot water immersion conditions).

The ambient temperature in the test was 20 ° C. ii) The results are shown in Table 2.

[0075]

[Table 2]

As shown in Table 2, the quick-curing adhesives of Examples 1 to 3 exhibited high adhesive strength under any of the following conditions: initial conditions, 24 hours at room temperature, 24 hours at room temperature + hot water immersion. showed that. In addition, under the condition of standing at room temperature for 24 hours,
The material rupture rates were all 100%.

In particular, Example 3 containing isocyanate
Has a high adhesive strength under the conditions of standing at room temperature for 24 hours and immersion in warm water. That is, the fast-curing adhesive of Example 3 had high water resistance. In addition, the quick-curing adhesive of Example 3 exhibited high bonding strength in each of the bonding methods (double-sided bonding method or single-sided bonding method).

On the other hand, the quick-curing adhesives of Comparative Examples 1 to 5
Although the adhesive strength and the material rupture rate were high under the conditions left at room temperature for 4 hours, the adhesive strength was very low under the initial conditions, the conditions left at room temperature for 24 hours and the conditions of immersion in warm water. Comparative Examples 6 and 7
The fast-curing adhesive of the initial conditions, 24 hours at room temperature conditions,
The adhesive strength and the material rupture rate were low under any of the conditions of standing at room temperature for 24 hours and immersion in hot water.

Measurement of Curing Speed i) Test Method The tests were performed on the fast-curing adhesives of Examples 1 to 3 and Comparative Examples 1 to 6 as follows.

100 g of the first agent is placed in a 200 ml beaker, and 20 g of the second agent is added thereto. Simultaneously with the addition of the second agent, the first agent and the second agent are stirred with a glass rod, and the time from the start of stirring until gelation is measured, and this time is defined as the curing speed.

The ambient temperature in the test was 20 ° C. ii) The results are shown in Table 3.

[0082]

[Table 3]

As shown in Table 3, the curing speeds of the fast-curing adhesives of Examples 1 to 3 were very short, 20 to 22 seconds. On the other hand, the curing speeds of the quick-curing adhesives of Comparative Examples 1 to 6 are as follows:
All were 35 seconds or more.

Flash Panel Adhesion Test i) Test Method The test was performed by flash bonding using the quick-curing adhesives of Examples 1 to 3 and Comparative Examples 1 to 7, and observing the bonded portion.

Specifically, a core material in which a particle board having a width of 5 cm is flashed and a face material (50 c
m × 100 cm), the second agent is applied to the plywood side of the face material at an application amount of about 30 g / m ^2, and the first agent is applied to the core particle board at an application amount of approximately 150 g / m ² . After the application, the core material and the face material are attached to each other, and immediately about 0.
Bonding was performed by pressing with a pressure of 5 MPa for 30 seconds.

After the press pressure was released, the peeling of the bonded portion was observed, and the evaluation was evaluated as で あ れ ば if it was good and × if peeling occurred. ii) The results are shown in Table 3. As shown in Table 3, when flash bonding was performed using the quick-curing adhesives of Examples 1 to 3, peeling and the like did not occur.

On the other hand, when flash bonding was performed using the fast-curing adhesives of Comparative Examples 1 to 7, peeling and the like occurred. V-cut adhesion test The test was performed by a method of performing V-cut adhesion using the quick-curing adhesives of Examples 1 to 3 and Comparative Examples 1 to 7 and observing the bonded portion.

Specifically, first, the second agent was applied at a coating amount of about 30 g / m ^{2 on} MDF (medium density fiberboard) having a V-groove, and the first agent was applied thereon from the coating amount of about 30 g / m ² . After applying at 150 g / m ^2, they were bonded and immediately pressed under a pressure of about 0.5 MPa for 30 seconds to perform bonding. After bonding, the peeling of the bonded portion was observed.
Was evaluated.

Ii) The results are shown in Table 3. As shown in Table 3, when V-cut bonding was performed using the fast-curing adhesives of Examples 1 to 3, peeling and the like did not occur. On the other hand, when V-cut bonding was performed using the quick-curing adhesives of Comparative Examples 1 to 7, peeling and the like occurred.

Water washing test of inner wall of pot used for production i) Test method For Examples 1, 2 and 4, the condition of the inner wall of the pot used for production of the first agent was observed after the production was completed, and the inner wall of the pot was observed. It was tested whether or not the deposits could be removed by washing with water.

Ii) The results are shown in Table 4.

[0092]

[Table 4]

As shown in Table 4, in Examples 1 and 2, what adhered to the inner wall of the kettle was an emulsion-like substance (resin component of the first agent), which was easily removed by washing with water. We were able to. Further, since the dry film of the resin does not adhere to the inner wall of the kettle, the problem that the dry film of the resin is mixed into the adhesive to form an agglomerate and cause a problem as a product does not occur.

In Example 4, when the acetoacetylated polyvinyl alcohol was mixed and dissolved, forcible external heating was performed from the beginning of the mixing, so that a dry film of the resin adhered to the inner wall of the kettle. Could not be removed.
It should be noted that the present invention is not limited to the above embodiment at all, and can be implemented in various embodiments without departing from the gist of the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09J 129/04 C08L 29/04

Claims (9)

(57) [Claims] 1. A fast-curing adhesive comprising: a first agent containing a resin emulsion and acetoacetylated polyvinyl alcohol; and a second agent containing a hydrazine derivative, wherein the first agent contains a hydrazine derivative. The sum of the weight ratio and the weight ratio of the acetoacetylated polyvinyl alcohol is in the range of 45 to 65% by weight, and the degree of polymerization of the acetoacetylated polyvinyl alcohol is in the range of 1000 to 2500. Fast curing adhesive to do. 2. The quick-curing adhesive according to claim 1, wherein the first agent contains an isocyanate compound. 3. A method for producing a quick-curing adhesive, comprising: a first agent containing a resin emulsion and acetoacetylated polyvinyl alcohol; and a second agent containing a hydrazine derivative, wherein the first agent is produced. A method for producing a quick-setting adhesive, comprising a step of stirring and mixing the powder of the acetoacetylated polyvinyl alcohol with the resin emulsion to dissolve the acetoacetylated polyvinyl alcohol in the mixture. 4. The method for producing a quick-curing adhesive according to claim 3, wherein the quick-curing adhesive is the quick-curing adhesive according to claim 1 or 2. 5. The method for producing a quick-setting adhesive according to claim 3, wherein the acetoacetylated polyvinyl alcohol is dissolved by heating. 6. The method for producing a quick-setting adhesive according to claim 5, wherein the heating is performed by internal mixing heat generated as the mixture is generated. 7. The method for producing a quick-curing adhesive according to claim 3, wherein an isocyanate is added to the mixture. 8. A bonding method using the quick-curing adhesive according to claim 1 or 2, wherein the first agent is applied to a surface of one member, and the second agent is applied to another one of the members. An application step of applying to the surface of the member, a surface of the one member to which the first agent is applied, and the other 1
A bonding step of bonding the first member and the other member so that the surface of the member to which the second agent is applied overlaps. 9. A bonding method using the quick-curing adhesive according to claim 1 or 2, wherein the first agent and the second agent are sequentially deposited and applied to the surface of one member. A coating step, and a bonding step of bonding the one member and the other member so that the surface of the one member on which the deposition coating is performed is a bonding surface with another member. And a bonding method comprising: